Anthraquinone vat dyestuffs



Patented May 2, 1950 AN THRAQUINON E VAT DYESTUFFS Walter Jenny, Reinach, near Basel, and Walter Kern, Sissach, Switzerland, assignors to Ciba Limited, Basel, Switzerland No Drawing.

Application December 6, 1948, Se-

rial No. 63,848. In Switzerland December 24,

3 Claims.

' According to the present invention, unexpectedly valuable vat dyestufis are made by treating with an acylating agent a l-acylaminol-aminoanthraquinone, and so selecting the acylating agent and the l-acylamino-4-aminoanthraquinone that one of the two acyl groups present in the final product is the residue of a benzene-1- carboxylic acid-3-dialkylsulphonamide and the other of such acyl groups is the residue of an aromatic carboxylic acid of the benzene series free from sulphonamido groups, and that a substituent is present at least in the anthraquinone nucleus or the aromatic nucleus of the residue of the carboxylic acid free from sulphonamido groups.

The 1-acylamino-e-aminoanthraquinones serving as starting materials can be obtained in known manner, for example, by monoacylating a 1:4-diaminoanthraquinone or by acylating a 1- aminol-nitroanthraquinone and subsequently reducing the nitro group The acylamino group in the 1-position may contain as an acyl residue, for example, the residue of a benzoic acid-3- dlalkylsulphonoamide. In the dialkylsulphona mido-group the two alkyl residues are advantageously of low molecular Weight, that is to say, they contain only few, for example, less than four, carbon atoms per alkyl residue. As examples there may be mentioned an N-diethylsulphonamido group and especially an N-dimethylsulphonamido group. The two. alkyl residues of a sulphonamido group may be connected together by a bridge member, for example, by an oxygen atom or a methylene group, as in the case of sulphon-morpholido and sulphon-piperidido groups.

- When a 1-(3-dialkylsulphonamido) -benzoy1amino-e-aminoanthraquinone is used as starting material it must be treated with an acylating agent which introduces the residue of an arcmatic carboxylic acid of the benzene series free from sulphonamido groups. As examples of such acylating agents there may be mentioned reactive functional derivatives of benzoic acid, especially the acid halides and preferably the acid chloride. The residue of the cyclic carboxylic acid may contain substituents for example, a halogen atom, an alkoxy group or another substituent, which is not harmful in vat dyestuffs, such as an alkyl group, a. cyano group or an alkylsulphone or 2 arylsulphone group, such substituent being present advantageously in paraposition to the carboxylic acid group.

The vat dyestuffs may be made in the reverse manner by using as the starting material a 1- acylamino-4-aminoanthraquinone containing the residue of a cyclic carboxylic acid free from sulphonamido groups (see, for example, the residues mentioned above). In this case there must be used an acylating agent which is capable of introducing the residue of a benzene-l-earboxylic acid-3-dialkylsulphonamide.

The components must also be so chosen that a substituent is present in the anthraquinone nucleus or in the aromatic nucleus of the carboxylic acid free from sulphonamido groups or in both nuclei. As such a substituent there comes into consideration, as mentioned above, for example, a cyano, alkyl or alkoxy group and especially a halogen atom. In many cases especially favourable results are obtained with a halogen atom, advantageously a chlorine atom, which is present in a B-position in the anthraquinone nucleus. preferably in the 6- or 7-position.

It will be apparent from the foregoing that there may be used as starting materials, for example, 1- (3' -dimethyl-sulphonamido) -benzoylamino-4-aminoanthraquinone and its 6- or 7- chloro-derivative, benzoylamino-4-aminoanthraquinone and its 6- or 'l-chloro-derivative, 1-(3'-su1phon-piperidido) -benzoy1amino-4-aminoanthraquinone and its 6- or 1-chloro-derivative. In many cases mixtures of aminoanthraquinone components may be used, which contain both the 6- and 'l-chloroderivative. These aminoanthraquinone components may be reacted, for example, with functional derivatives of the following acids: l-methoxybenzoic acid, 4-bromoand especially 4,-ch1oro-benzoic acid. When the starting material is substituted in the anthraquinone nucleus, there may be used a functional derivative of benzoic acid itself, especially benzoyl chloride.

Conversely, there come into consideration the following starting materials: l-benzoylamino-eamino-6- or -7-chloranthraquinone, 1-(4'-methoxy) -benzoylamino-4-aminoanthraquinone or its 6- or Z-chloro-derivative, 1-(4'-chloroor -4- bromo) -benzoylamino-4-aminoanthraquinone or its 6- or 'I-chloro-derivative. Such aminoanthra- 1- (3-sulphon-morpho1ido) quinone components may be reacted, for example, with functional derivatives, advantageously acid chlorides of the following acids: benzoic acid-3- dimethysulphonainide, benzoic acid-3-diethylsulphonarnide, henzoic acid-3-sulphon-morpholide, benzoic acid 3 sulphcn piperidide or 4- chlorobenzoic acid-3-dimethyl-sulphonamide The treatment of the aminoanthraquinone components with acylating agents may be con ducted with advantage in an inert solvent or diluent, advantageously of relatively high boiling point such as nitrobenzene or mono-, dior tri. chlorobenzene or naphthalene, generally at a high temperature, for example, 100' C. to the boiling point of the solvent or diluent in question.

The vat dyestuffs obtained by the process of the invention correspond to the general formula NHCOR1 in whiohRr -CO represents the residue of aromatic carboxylic acid of the benzene series free from sulphonamido groups, X represents a dialkylsulphonamido group, one 1, stands for hydrogen and the other y for hydrogen or for a sub- 0 stituent consisting 'of a halogen atom and R2 represents a benzene nucleusto which the CO- group and the group X are bound in the1t3-position, and a substituent is present at least in the anthraquinone nucleus or in the nucleus R1.

These vat 'dyestufis can be used as pigment dyestuffs'or'for dyeing and'espeoially for printing a very wide variety of fibers,1such as wool, leather or silk, but principally vegetable cellulosic fibers such as linen, cotton, artificial silk or'staple fibers of regenerated cellulose. They may also be used in the'iorm of their leuco ester salts (especially sulfuric acid esters), obtainable by methods known in connection with dyestuffs of this class. The following examples illustrate the invention, the parts and percentages being by weight unless otherwise stated and the relationship of parts by weight to parts by volume being the same a that of the kilogram to the liter:

Example 1 I. SOLN /O GET-CH2 is separated by filtering with suction, well washed with boiling alcohol and dried. It dissolves in concentrated sulfuric acid with a red-violet color- 4 ation and dyes cotton from a violet vat very fast, pure bluish-pink tints.

Benzoic acid-3-sulphon-morpholide may be prepared as follows:

11 parts of benzoic acid-3-sulphochloride are added slowly with thorough stirring to a solution of 17 parts of morpholine in 150 parts of Water at ordinary temperature. When the addition is complete, the temperature is raised, While stirring, to 50 C. in the course of 2 hours, and then the whole is allowed to cool. The sulphon-morpholide precipitated with'dilute hydrochloric acid forms a White crystalline powde Upon recrystallisation from water the product is obtained in the form of handsome colorless lamellae.

1 benzoylamino 4 amino 6 chloranthraquinone can be prepared by the benzoylation and subsequent reduction of l-amino-nitrochloranthraquinone (compare United States Patent No. 2,134,654, Example 3). 4-nitro-6-chloranthraquinone are suspended in 15 parts of l-amino- 150 parts of dry ortho-dichlorobenzene and, after the addition of 15 parts of benzoyl chloride, the whole is stirred for 3 hours at the boil. The yellow benzoylamino-compound, which is isolated 'by cooling, filtration, and Washing with alcohol issuspended in ,7 times its weightof ortho-dichlo robenzene, mixed with twice its weight of-phenylhydrazine and stirred for 1 hour at 135.- Cl Upon cooling, 1-benzeylamino-l-amino-6-chloranthraquinone crystallises in violet needles.

Example 2 27.5 parts of benzoic acid-3-sulphon;morpho lide are suspended in 380 parts .of .dry nitrobenis separated by filtering with suction, washed well with boiling alcohol and dried. It dissolves in concentrated sulfuric acid with an olive brown coloration and dyes cotton from a red-violet vat very fast bluish-pink tints.

1 (para. methoxybenzoylamino) fl-amino-6-- chloranthraquinone may be prepared, as 'described 'in Example 1, by acylating l-ai'ninolnitro-6-chloranthraquinone with para-methoxy-- benzoyl chloride and subsequently reducing thenitro-group.

amide are suspended in 270 parts of dry initros:

benzene and, after-the addition of 12 parts of thionyl chloride -and-0.5 part"of pyridine, stirred 'When recrystallised from OPthO- dichlorobenzene the compound forms small red-" a for 1% hours-at 70-80 C. There are then added 30 parts of 1-benzoylamino-4-amino-6-chlor" anthraquinone and the whole is stirred for 2 hours at 125-130 C. The dyestuff which separates upon cooling in the form of small red needles and which corresponds to the probable formula II V HNO

Example 4 55 parts of 1-amino-4-(3-dimethylsu1pl1onamido-benzoylamino) -7chloranthraquinone are suspended in 400 parts of dry nitrobenzene and, after the addition of 45 parts of benzoyl chloride, stirred for 3 hours at 125-135 C. The dyestuif, which precipitates upon cooling in the form of small red crystals and which corresponds to the V probable formula:

SOgN

ENG 0- is separated by filtering with suction washed well with boiling alcohol and dried. It dissolves in concentrated sulfuric acid with a red coloration and dyes cotton from a violet vat very fast pure pink tints.

1-amino-4- (3 -dimethylsulphonamido-benzoylamino)-7-ch10ranthraquinone may be prepared, for example, in the following manner: 46 parts of benzoic acid 3 dimethylsulphonamide are suspended in 280 parts of dry nitrobenzene and after the addition of 30 parts of thionyl chloride and 0.5 part of pyridine stirred for 1 hours at 70-80" C. The whole is then mixed with 60 parts of 1-amino-4-nitro-6-chloranthraquinone and stirred for a further 2 hours at 125-135 C. The 1-nitro 4 (3-dimethyl-sulphonamido-benzoylamino) 7 chloranthraquinone, which precipitates upon cooling in the form of yellow crystals is separated by filtering with suction, washed well with hot alcohol, and then suspended in 10 times its Weight of ortho-dichlorobenzene and, after the addition of 3 times its weight of phenylhydrazine, stirred for 1 hour at 135-145 C. Upon cooling, 1-amino-4-(3'-dimethy1-sulphonamidobenzoylamino) 7 chloranthraquinone precipitates in the form of violet crystals.

Example 5 23 parts of benzoic acid-3-dimethylsulphonamide are suspended in 320 parts of dry nitrobenzene and after the addition of parts of thionyl chlorideand 0.5 part of'pyridine, stirred for 1 hours at 70-80 C. The whole isthen mixed with ,37. parts of 1-:(4'-chlorobenzoylamino) -4-aminoanthraquinone, and stirred for a further 2 hours at .120-130 C. The dyestuff, which precipitates upon cooling in the form of orange red crystals and which corresponds to the probable formula v on. HNCO-- v is separated by filtering with suction and washed well with boiling alcohol. It dissolves in concentrated hydrochloric acid with a red coloration and dyes cotton from a violet vat fast orange colored tints.

Example 6 27 parts of 4-chlorobenzoic acid-S-dimethylsulphonamicle are suspended in 320 parts of dry nitrobenzene and, after the addition of 16 parts of thionyl chloride and 0.5 part of pyridine, stirred for 1 /2 hours at -100 C. The whole is then mixed with 3'7 parts of 1-am:lno-4-(3- chlorobenzoylamino)-anthraquinone and stirred for a further 2 hours at 120-130" C. The dyestuif which precipitates upon cooling in the form of orange colored crystals and which corresponds to the probable formula 0 Erica-Q SO2N is separated by filtering with suction, washed with boiling alcohol and dried. It dissolves in concentrated sulfuric acid with a red coloration and dyes cotton orange tints from a violet vat.

4-chlorobenzoic acid-3-dimethylsulphonamide is prepared in the same manner as benzoic acid 3 sulphon morpholide (see Example 1) from the corresponding sulphochloride and an excess of dimethylamine in aqueous solution.

Example 7 1 part of the dyestuff obtained as described in Example 1 is vatted at 50 C. in parts of water by the addition of 4 parts by volume of caustic soda solution of 36 B. and 2 parts of sodium hydrosulphite. The resulting stock vat is added to a dyebath consisting of 3000 parts of water, 8 parts by volume of caustic soda solution of 36 B. and 3 parts of sodium hydrosulphite. 100 parts of cotton are entered at 25 C., 45 parts of sodium chloride are added after 15 minutes, and dyeing is carried on at 25-30" C. for 1 hour. The cotton is then finished in the usual manner. After soaping there are obtained very fast bluish pink tints.

Reference is made to the applicants copending application, Ser. No. 63,847, filed on even date herewith, which claims subject matter disclosed but not claimed in the instant application.

2;5Q6;D25 V "i fiavingfihus described thexmventl'onywhatls 'A'vat dyestufl' which corresponds tdfth claimed is: formula. V

1. vAvat-vslyestufi which corresponds to the I m VIIIQFOO HNOO B O :N (alkyl) I h V SIN(81kY1)| in which X stands for a halogen atom.

2. The vat dyestufi of the formula WALTER JENNY.

1-5 WALTER KERN. o EN00- 3-01 I I REFERENCES CITED The following references are, of record in the; me of this patent: UNITED STATES PATENTS NC o- Nmnber Name Date 2,190,751 Zerweck et a1. Feb.:20, 1940 

1. A VAT DYESTUFF WHICH CORRESPONDS TO THE FORMULA 